Electroactive materials

ABSTRACT

There is provided an electroactive material having Formula I 
     
       
         
         
             
             
         
       
     
     wherein:
         Q is the same or different at each occurrence and can be O, S, Se, Te, NR, SO, SO 2 , or SiR 3 ;   R is the same or different at each occurrence and can be hydrogen, alkyl, aryl, alkenyl, or alkynyl;   R 1  through R 8  are the same or different and can be hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO 3 R 2 , —OPO 3 R 2 , or CN.

RELATED APPLICATION

This application claims priority under 35 U.S.C. § 119(e) fromProvisional Application No. 61/013,530 filed on Dec. 13, 2007 which isincorporated by reference in its entirety.

BACKGROUND INFORMATION

1. Field of the Disclosure

This disclosure relates in general to electroactive materials, theirsynthesis, and their use in electronic devices.

2. Description of the Related Art

Organic electronic devices that emit light, such as light-emittingdiodes that make up displays, are present in many different kinds ofelectronic equipment. In all such devices, an organic active layer issandwiched between two electrical contact layers. At least one of theelectrical contact layers is light-transmitting so that light can passthrough the electrical contact layer. The organic active layer emitslight through the light-transmitting electrical contact layer uponapplication of electricity across the electrical contact layers.Additional electroactive layers may be present between thelight-emitting layer and the electrical contact layer(s).

It is well known to use organic electroluminescent compounds as theactive component in light-emitting diodes. Simple organic molecules,such as anthracene, thiadiazole derivatives, and coumarin derivativesare known to show electroluminescence. In some cases these smallmolecule materials are present as a dopant in a host material to improveprocessing and/or electronic properties.

There is a continuing need for new electroactive materials forelectronic devices.

SUMMARY

There is provided an electroactive material having Formula I:

wherein:

-   -   Q is the same or different at each occurrence and is        independently selected from the group consisting of O, S, SO,        SO₂, Se, Te, NR, BR, PR, PO, PO₂, and SiR₂;    -   R is the same or different at each occurrence and is        independently selected from the group consisting of hydrogen,        alkyl, aryl, alkenyl, and alkynyl;    -   R¹ through R⁸ are the same or different and are independently        selected from the group consisting of hydrogen, alkyl, aryl,        halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino,        alkylthio, phosphino, silyl, —COR, —COOR, —PO₃R₂, —OPO₃R₂, and        CN.

There is also provided a polymer comprising at least one repeating unithaving Formula I, wherein R1 and R3 or R5 and R8 represent points ofattachment to the polymer backbone.

There is also provided an organic electronic device comprising a firstelectrical contact, a second electrical contact and at least oneelectroactive layer therebetween, the electroactive layer comprising theabove electroactive material.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated in the accompanying figures to improveunderstanding of concepts as presented herein.

FIG. 1 includes an illustration of one example of an organiclight-emitting diode.

Skilled artisans appreciate that objects in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the objects in the figures may beexaggerated relative to other objects to help to improve understandingof embodiments.

DETAILED DESCRIPTION

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims. The detailed description first addresses Definitions andClarification of Terms followed by the Electroactive Materials,Electroactive Polymers, Devices, and finally Examples.

1. Definitions and Clarification of Terms

Before addressing details of embodiments described below, some terms aredefined or clarified.

The term “alkenyl” is intended to mean a group derived from an aliphatichydrocarbon having at least one carbon-carbon double bond.

The term is intended to include heteroalkyl groups.

The term “alkoxy” is intended to mean a group having the formula —OR,which is attached via the oxygen, where R is an alkyl.

The term “alkyl” is intended to mean a group derived from a saturatedaliphatic hydrocarbon and includes a linear, a branched, or a cyclicgroup. In some embodiments, an alkyl has from 1-20 carbon atoms. Theterm is intended to include heteroalkyl groups. In some embodiments, theheteroalkyl groups have from 1-20 carbon atoms and from 1-5 heteroatoms.

The term “alkylthio” is intended to mean a group having the formula —SR,which is attached via the sulfur, where R is an alkyl.

The term “alkynyl” is intended to mean a group derived from an aliphatichydrocarbon having at least one carbon-carbon triple bond.

The term “blue luminescent material” is intended to mean a materialcapable of emitting radiation that has an emission maximum at awavelength in a range of approximately 400-500 nm. “Deep blue” isintended to refer to 450-490 nm.

The term “charge transport,” when referring to a layer, material,member, or structure is intended to mean such layer, material, member,or structure facilitates migration of such charge through the thicknessof such layer, material, member, or structure with relative efficiencyand small loss of charge. Although light-emitting materials may alsohave some charge transport properties, the term “charge transport layer,material, member, or structure” is not intended to include a layer,material, member, or structure whose primary function is light emission.

The term “electroactive” as it refers to a layer or a material, isintended to indicate a layer or material which electronicallyfacilitates the operation of the device. Examples of active materialsinclude, but are not limited to, materials which conduct, inject,transport, or block a charge, where the charge can be either an electronor a hole, or materials which emit radiation or exhibit a change inconcentration of electron-hole pairs when receiving radiation. Examplesof inactive materials include, but are not limited to, planarizationmaterials, insulating materials, and environmental barrier materials.

The terms “emitter” and “luminescent material” are intended to mean amaterial that emits light when activated by an applied voltage (such asin a light-emitting diode or light-emitting electrochemical cell).

The prefix “hetero” indicates that one or more carbon atoms has beenreplaced with a different atom. In some embodiments, the heteroatom isO, N, S, or a combination thereof.

The term “layer” is used interchangeably with the term “film” and refersto a coating covering a desired area. The term is not limited by size.The area can be as large as an entire device or as small as a specificfunctional area such as the actual visual display, or as small as asingle sub-pixel. Layers and films can be formed by any conventionaldeposition technique, including vapor deposition, liquid deposition(continuous and discontinuous techniques), and thermal transfer.Continuous deposition techniques, include but are not limited to, spincoating, gravure coating, curtain coating, dip coating, slot-diecoating, spray coating, and continuous nozzle coating. Discontinuousdeposition techniques include, but are not limited to, ink jet printing,gravure printing, and screen printing.

The term “organic electronic device” or sometimes just “electronicdevice” is intended to mean a device including one or more organicsemiconductor layers or materials.

The term “phosphino” is intended to mean the group R₂P—, attached viathe phosphorus and where R is alkyl or aryl.

The term “polymer” is intended to mean a material having at least onerepeating monomeric unit. The term includes homopolymers having only onekind of monomeric unit, and copolymers having two or more differentmonomeric units. Copolymers are a subset of polymers. In one embodiment,a polymer has at least 5 repeating units.

The term “silyl” is intended to mean the group R₃Si—, attached via thesilicon and where R is alkyl.

Unless otherwise indicated, all groups can be substituted orunsubstituted.

An optionally substituted group, such as, but not limited to, alkyl oraryl, may be substituted with one or more substituents which may be thesame or different. Suitable substituents include alkyl, aryl, nitro,cyano, halo, hydroxy, carboxy, alkenyl, alkynyl, cycloalkyl, heteroaryl,alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl,perfluoroalkoxy, arylalkyl, thioalkoxy, —S(O)₂—N(R′)(R″),—C(═O)—N(R′)(R″), (R′)(R″)N-alkyl, (R′)(R″)N-alkoxyalkyl,(R′)(R″)N-alkylaryloxyalkyl, —S(O)_(x)-aryl (where s=0-2) or—S(O)_(s)-heteroaryl (where s=0-2).

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of theelements use the “New Notation” convention as seen in the CRC Handbookof Chemistry and Physics, 81^(st) Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specificmaterials, processing acts, and circuits are conventional and may befound in textbooks and other sources within the organic light-emittingdiode display, photodetector, photovoltaic, and semiconductive memberarts.

2. Electroactive Materials

The new electroactive materials described herein have Formula I:

wherein:

-   -   Q is the same or different at each occurrence and is        independently selected from the group consisting of O, S, SO,        SO₂, Se, Te, NR, BR, PR, PO, PO₂, and SiR₂;    -   R is the same or different at each occurrence and is        independently selected from the group consisting of hydrogen,        alkyl, aryl, alkenyl, and alkynyl;    -   R¹ through R⁸ are the same or different and are independently        selected from the group consisting of hydrogen, alkyl, aryl,        halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino,        alkylthio, phosphino, silyl, —COR, —COOR, —PO₃R₂, —OPO₃R₂, and        CN.

In some embodiments, Q is selected from the group consisting of O and S.In some embodiments, Q is O.

In some embodiments, at least one of R¹ and R³ is not hydrogen.

In some embodiments, at least one of R¹ and R³ is selected from thegroup consisting of alkyl, aryl, and diarylamino. In some embodiments,R¹ and R³ are the same.

In some embodiments, at least one of R² and R⁴ is not hydrogen.

In some embodiments, at least one of R² and R⁴ is selected from thegroup consisting of alkyl, aryl, and diarylamino. In some embodiments,R² and R⁴ are the same.

In some embodiments, at least one of R⁵, R⁶, R⁷, and R⁸ is not hydrogen.In some embodiments, at least one of R⁵, R⁶, R⁷, and R⁸ is selected fromthe group consisting of alkyl, aryl, and diarylamino. In someembodiments, R⁵ and R⁸ are the same. In some embodiments, R⁶ and R⁷ arethe same.

In some embodiments, at least one of R¹ through R⁸ is an aryl group.Examples of aryl groups include, but are not limited to Ar1 to Ar92,shown in Table 1.

TABLE 1 Electroactive Compounds Ar Chemical Structure of substituent Ar1

Ar2

Ar3

Ar4

Ar5

Ar6

Ar7

Ar8

Ar9

Ar10

Ar11

Ar12

Ar13

Ar14

Ar15

Ar16

Ar17

Ar18

Ar19

Ar20

Ar21

Ar22

Ar23

Ar24

Ar25

Ar26

Ar27

Ar28

Ar29

Ar30

Ar31

Ar32

Ar33

Ar34

Ar35

Ar36

Ar37

Ar38

Ar39

Ar40

Ar41

Ar42

Ar43

Ar44

Ar45

Ar46

Ar47

Ar48

Ar49

Ar50

Ar51

Ar52

Ar53

Ar54

Ar55

Ar56

Ar57

Ar58

Ar59

Ar60

Ar61

Ar62

Ar63

Ar64

Ar65

Ar66

Ar67

Ar68

Ar69

Ar70

Ar71

Ar72

Ar73

Ar74

Ar75

Ar76

Ar77

Ar78

Ar79

Ar80

Ar81

Ar82

Ar83

Ar84

Ar85

Ar86

Ar87

Ar88

Ar89

Ar90

Ar91

Ar92

In some embodiments, the electroactive material is selected fromCompounds 1 to Compound 13, below:

The electroactive materials described herein, can be prepared usingstandard synthetic techniques, as illustrated in the Examples.

3. Polymers

In some embodiments, the compounds having Formula I are polymerized toform polymeric electroactive materials. In some embodiments, the polymerhas at least one monomeric unit selected from the group consisting ofFormula II, Formula III, or combinations thereof.

wherein:

-   -   Q is the same or different at each occurrence and is        independently selected from the group consisting of O, S, SO,        SO₂, Se, Te, NR, BR, PR, PO, PO₂, and SiR₂;    -   R is the same or different at each occurrence and is        independently selected from the group consisting of hydrogen,        alkyl, aryl, alkenyl, and alkynyl; and    -   R¹ through R⁸ are the same or different and are independently        selected from the group consisting of hydrogen, alkyl, aryl,        halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino,        alkylthio, phosphino, silyl, —COR, —COOR, —PO₃R₂, —OPO₃R₂, and        CN.

In some embodiments of Formulae II and III, Q is O or S. In someembodiments of Formula II, Q is O.

In some embodiments of Formulae II and III, at least one of R² and R⁴ isnot hydrogen. In some embodiments, at least one of R² and R⁴ is selectedfrom the group consisting of alkyl, aryl, and diarylamino. In someembodiments, R² and R⁴ are the same.

In some embodiments of Formulae II, at least one of R⁵, R⁶, R⁷, and R⁸is not hydrogen. In some embodiments, at least one of R⁵, R⁶, R⁷, and R⁸is selected from the group consisting of alkyl, aryl, and diarylamino.In some embodiments, R⁵ and R⁸ are the same. In some embodiments, R⁶ andR⁷ are the same.

In some embodiments of Formula III, at least one of R¹ and R³ is nothydrogen. In some embodiments, at least one of R¹ and R³ is selectedfrom the group consisting of alkyl, aryl, and diarylamino. In someembodiments, R¹ and R³ are the same.

In some embodiments of Formula III, at least one of R⁶ and R⁷ is nothydrogen. In some embodiments, at least one of R⁶ and R⁷ is selectedfrom the group consisting of alkyl, aryl, and diarylamino. In someembodiments, R⁶ and R⁷ are the same.

In some embodiments, the polymer is a homopolymer of Formula II orFormula III, having two or more monomeric units. In some embodiments,the polymer is a copolymer of two or more monomeric units having FormulaII with different substituents. In some embodiments, the polymer is acopolymer of two or more monomeric units having Formula III withdifferent substituents. In some embodiments, the polymer is a copolymerhaving monomeric units of Formula II and monomeric units of Formula III.

In some embodiments, the polymer is a copolymer having Formula IV or V:

wherein:

-   -   Ar is the same or different at each occurrence and is an        aromatic unit;    -   Q is the same or different at each occurrence and is        independently selected from the group consisting of O, S, SO,        SO₂, Se, Te, NR, BR, PR, PO, PO₂, and SiR₂;    -   R is the same or different at each occurrence and is        independently selected from the group consisting of hydrogen,        alkyl, aryl, alkenyl, and alkynyl;    -   R¹ through R⁸ are the same or different and are independently        selected from the group consisting of hydrogen, alkyl, aryl,        halogen, hydroxyl, aryloxy, alkoxy, alkenyl, alkynyl, amino,        alkylthio, phosphino, silyl, —COR, —COOR, —PO₃R₂, —OPO₃R₂, and        CN; and    -   a and b represent mole fractions, such that a+b=1.

The copolymers can be random, alternating, or block copolymers.

Ar is an aromatic unit. In some embodiments, Ar has from 1-5 aromaticrings, which can be joined together by one or more bonds, or fusedtogether. In some embodiments, Ar is selected from the group consistingof Ar1 through Ar 92 in Table 1, where the groups have a second point ofattachment on one of the aromatic rings. In some embodiments, Ar isselected from the group consisting of phenylene, naphthylene,biphenylene, binaphthylene, anthracenylene, fluorenylene, diarylamineand combinations thereof. The diarylamine monomeric unit is joined tothe polymer backbone via the nitrogen and a carbon on one of the arylgroups. In some embodiments, Ar is further substituted with one or moregroups selected from the group consisting of alkyl, aryl, anddiarylamino. In some embodiments, Ar is the same at each occurrence. Insome embodiments, two different Ar units are present.

In some embodiments of Formulae III, Q is O or S. In some embodiments ofFormulae III, Q is O.

In some embodiments of Formulae IV and V, at least one of R² and R⁴ isnot hydrogen. In some embodiments, at least one of R² and R⁴ is selectedfrom the group consisting of alkyl, aryl, and diarylamino. In someembodiments, R² and R⁴ are the same.

In some embodiments of Formula IV, at least one of R⁵, R⁶, R⁷, and R⁸ isnot hydrogen. In some embodiments, at least one of R⁵, R⁶, R⁷, and R⁸ isselected from the group consisting of alkyl, aryl, and diarylamino. Insome embodiments, R⁵ and R⁸ are the same. In some embodiments, R⁶ and R⁷are the same.

In some embodiments of Formula V, at least one of R¹ and R³ is nothydrogen. In some embodiments, at least one of R¹ and R³ is selectedfrom the group consisting of alkyl, aryl, and diarylamino. In someembodiments, R¹ and R³ are the same.

In some embodiments of Formula V, at least one of R⁶ and R⁷ is nothydrogen. In some embodiments, at least one of R⁶ and R⁷ is selectedfrom the group consisting of alkyl, aryl, and diarylamino. In someembodiments, R⁶ and R⁷ are the same.

In some embodiments of Formulae IV and V, a is at least 0.3. In someembodiments, a is at least 0.5. In some embodiments, a is at least 0.8.In some embodiments, a is 0.3 to 0.7 and b is 0.3 to 0.7.

The polymers can be made using any technique that will yield a C—C orC—N bond and result in polymerization. A variety of such synthetictechniques are known, such as Suzuki, Yamamoto, Stille, andHartwig-Buchwald coupling.

In Yamamoto polymerization, for example, monomers having Cl, Br, I, ortoslyate functional groups, are added to a solution of a Ni(0) compoundin an inert solvent. Typically, a nickel (0) cyclooctadiene complex isused in the presence of a 2,2′-bipyridine in a solvent such as DMF. Thereaction is generally carried out at temperatures in the range of 60-80°C., and the resulting polymers isolated using known techniques, such asprecipitation. This has been described in Yamamoto, Progress in PolymerScience, Vol. 17, p 1153 (1992)

In Suzuki polymerization, for example, monomers having boronic acidfunctional groups are polymerized with monomers having halide ortosylate functional groups in coupling reactions using Pd(0) catalysts.Alternatively, monomers having both types of functional groups can beused. The monomers may be commercially available, or can be preparedusing known synthetic procedures. For example, monomers having brominefunctional groups can be synthesized by bromination of an aromaticcompound in chloroform. Monomers having boronic acid functional groupscan be synthesized, for example, by reaction a bromo-aromatic compoundwith an organolithium reagent, then quenching the reaction withtrimethylborate.

Some examples of polymers having one of Formulae II through V include,but are not limited to Compound 14 to Compound 18 below:

4. Devices

Organic electronic devices that may benefit from having one or morelayers comprising the electroactive materials described herein include,but are not limited to, (1) devices that convert electrical energy intoradiation (e.g., a light-emitting diode, light emitting diode display,or diode laser), (2) devices that detect signals through electronicsprocesses (e.g., photodetectors, photoconductive cells, photoresistors,photoswitches, phototransistors, phototubes, IR detectors), (3) devicesthat convert radiation into electrical energy, (e.g., a photovoltaicdevice or solar cell), and (4) devices that include one or moreelectronic components that include one or more organic semi-conductorlayers (e.g., a transistor or diode).

One illustration of an organic electronic device structure is shown inFIG. 1. The device 100 has a first electrical contact layer, an anodelayer 110 and a second electrical contact layer, a cathode layer 160,and a photoactive layer 140 between them. Adjacent to the anode is abuffer layer 120. Adjacent to the buffer layer is a hole transport layer130, comprising hole transport material. Adjacent to the cathode may bean electron transport layer 150, comprising an electron transportmaterial. As an option, devices may use one or more additional holeinjection or hole transport layers (not shown) next to the anode 110and/or one or more additional electron injection or electron transportlayers (not shown) next to the cathode 160.

In one embodiment, the different layers have the following range ofthicknesses: anode 110, 500-5000 Å, in one embodiment 1000-2000 Å;buffer layer 120, 50-2000 Å, in one embodiment 200-1000 Å; holetransport layer 120, 50-2000 Å, in one embodiment 200-1000 Å;photoactive layer 130, 10-2000 Å, in one embodiment 100-1000 Å; layer140, 50-2000 Å, in one embodiment 100-1000 Å; cathode 150, 200-10000 Å,in one embodiment 300-5000 Å. The location of the electron-holerecombination zone in the device, and thus the emission spectrum of thedevice, can be affected by the relative thickness of each layer. Thedesired ratio of layer thicknesses will depend on the exact nature ofthe materials used.

The electroactive materials described herein can be used as chargetransport material, as photoactive material, or as a host for anotherphotoactive material.

a. Photoactive Layer

The electroactive materials described herein are particularly suited foruse in the photoactive layer 140. They can be present alone and functionas the photoactive material, or they can be present as either a host ordopant. The term “dopant” is intended to mean a material, within a layerincluding a host material, that changes the electronic characteristic(s)or the targeted wavelength(s) of radiation emission, reception, orfiltering of the layer compared to the electronic characteristic(s) orthe wavelength(s) of radiation emission, reception, or filtering of thelayer in the absence of such material. The term “host material” isintended to mean a material, usually in the form of a layer, to which adopant may or may not be added. The host material may or may not haveelectronic characteristic(s) or the ability to emit, receive, or filterradiation.

In some embodiments, they function as the photoactive material. In someembodiments, when used as emissive materials, the compounds emit a colorranging from blue to green. The electroactive materials described hereincan be used alone, in combination with other luminescent materials, oras a dopant in a host material. In some embodiments, the electroactivematerials are used as a host material for one or more other emissivematerials.

In some embodiments, the electroactive materials described herein areused as a dopant in a host material. In some embodiments, the host is abis-condensed cyclic aromatic compound.

In some embodiments, the host is an anthracene derivative compound. Insome embodiments the compound has the formula:

An-L-An

where:

An is an anthracene moiety;

L is a divalent connecting group.

In some embodiments of this formula, L is a single bond, —O—, —S—,—N(R)—, or an aromatic group. In some embodiments, An is a mono- ordiphenylanthryl moiety.

In some embodiments, the host has the formula:

A-An-A

where:

An is an anthracene moiety;

A is an aromatic group.

In some embodiments, the host is a diarylanthracene. In some embodimentsthe compound is symmetrical and in some embodiments the compound isnon-symmetrical.

In some embodiments, the host has the formula:

where:

A¹ and A² are the same or different at each occurrence and are selectedfrom the group consisting of H, an aromatic group, and an alkenyl group,or A may represent one or more fused aromatic rings;

p and q are the same or different and are an integer from 1-3. In someembodiments, the anthracene derivative is non-symmetrical. In someembodiments, p=2 and q=1. In some embodiments, at least one of A¹ and A²is a naphthyl group.

In some embodiments, the host is selected from the group consisting of

and combinations thereof.b. Other Device Layers

The other layers in the device can be made of any materials which areknown to be useful in such layers.

The anode 110 is an electrode that is particularly efficient forinjecting positive charge carriers. It can be made of, for examplematerials containing a metal, mixed metal, alloy, metal oxide ormixed-metal oxide, or it can be a conducting polymer, and mixturesthereof. Suitable metals include the Group 11 metals, the metals inGroups 4, 5, and 6, and the Group 8-10 transition metals. If the anodeis to be light-transmitting, mixed-metal oxides of Groups 12, 13 and 14metals, such as indium-tin-oxide, are generally used. The anode may alsocomprise an organic material such as polyaniline as described in“Flexible light-emitting diodes made from soluble conducting polymer,”Nature vol. 357, pp 477 479 (11 Jun. 1992). At least one of the anodeand cathode should be at least partially transparent to allow thegenerated light to be observed.

The buffer layer 120 comprises buffer material and may have one or morefunctions in an organic electronic device, including but not limited to,planarization of the underlying layer, charge transport and/or chargeinjection properties, scavenging of impurities such as oxygen or metalions, and other aspects to facilitate or to improve the performance ofthe organic electronic device The buffer layer can be formed withpolymeric materials, such as polyaniline (PANI) orpolyethylenedioxythiophene (PEDOT), which are often doped with protonicacids. The protonic acids can be, for example, poly(styrenesulfonicacid), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), and the like.

The buffer layer can comprise charge transfer compounds, and the like,such as copper phthalocyanine and thetetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ).

In some embodiments, the buffer layer comprises at least oneelectrically conductive polymer and at least one fluorinated acidpolymer.

In some embodiments, the buffer layer is made from an aqueous dispersionof an electrically conducting polymer and a colloid-forming polymericacid. Such materials have been described in, for example, published U.S.patent applications 2004-0102577, 2004-0127637, and 2005-0205860.

The hole transport layer 130 is a charge transport layer whichfacilitates the migration of positive charges. In some embodiments, thehole transport layer comprises the new electroactive material describedherein. In some embodiments, the hole transport layer consistsessentially of the new electroactive material described herein. In someembodiments, the hole transport layer comprises the new electroactivepolymer described herein. In some embodiments, the hole transport layerconsists essentially of the new electroactive polymer described herein.

Examples of other hole transport materials for the hole transport layerhave been summarized for example, in Kirk-Othmer Encyclopedia ofChemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y.Wang. Both hole transporting small molecules and polymers can be used.Commonly used hole transporting molecules include, but are not limitedto: 4,4′,4″-tris(N,N-diphenyl-amino)-triphenylamine (TDATA);4,4′,4″-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA);N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD); 4,4′-bis(carbazol-9-yl)biphenyl (CBP);1,3-bis(carbazol-9-yl)benzene (mCP); 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC);N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD); tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA);α-phenyl-4-N,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehydediphenylhydrazone (DEH); triphenylamine (TPA);bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP);1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB);N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB);N,N′-bis(naphthalen-1-yl)-N,N′-bis-(phenyl)benzidine (α-NPB); andporphyrinic compounds, such as copper phthalocyanine. Commonly used holetransporting polymers include, but are not limited to,polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophenes),polyanilines, and polypyrroles. It is also possible to obtain holetransporting polymers by doping hole transporting molecules such asthose mentioned above into polymers such as polystyrene andpolycarbonate.

In some embodiments, the hole transport layer comprises a hole transportpolymer. In some embodiments, the hole transport polymer is adistyrylaryl compound. In some embodiments, the aryl group is has two ormore fused aromatic rings. In some embodiments, the aryl group is anacene. The term “acene” as used herein refers to a hydrocarbon parentcomponent that contains two or more ortho-fused benzene rings in astraight linear arrangement.

In some embodiments, the hole transport polymer is an arylamine polymer.In some embodiments, it is a copolymer of fluorene and arylaminemonomers.

In some embodiments, the polymer has crosslinkable groups. In someembodiments, crosslinking can be accomplished by a heat treatment and/orexposure to UV or visible radiation. Examples of crosslinkable groupsinclude, but are not limited to vinyl, acrylate, perfluorovinylether,1-benzo-3,4-cyclobutane, siloxane, and methyl esters. Crosslinkablepolymers can have advantages in the fabrication of solution-processOLEDs. The application of a soluble polymeric material to form a layerwhich can be converted into an insoluble film subsequent to deposition,can allow for the fabrication of multilayer solution-processed OLEDdevices free of layer dissolution problems.

Examples of crosslinkable polymers can be found in, for example,published US patent application 2005-0184287 and published PCTapplication WO 2005/052027.

In some embodiments, the hole transport layer comprises a polymer whichis a copolymer of 9,9-dialkylfluorene and triphenylamine. In someembodiments, the polymer is a copolymer of 9,9-dialkylfluorene and4,4′-bis(diphenylamino)biphenyl. In some embodiments, the polymer is acopolymer of 9,9-dialkylfluorene and TPB. In some embodiments, thepolymer is a copolymer of 9,9-dialkylfluorene and NPB. In someembodiments, the copolymer is made from a third comonomer selected from(vinylphenyl)diphenylamine and 9,9-distyrylfluorene or9,9-di(vinylbenzyl)fluorene.

The electron transport layer 150 is a charge transport layer whichfacilitates the migration of negative charges. In some embodiments, theelectron transport layer comprises the new electroactive materialdescribed herein. In some embodiments, the electron transport layercomprises the new electroactive copolymer described herein. In someembodiments, the electron transport layer consists essentially of thenew electroactive copolymer described herein.

The electron transport layer 150 is a layer which facilitates migrationof negative charges through the thickness of the layer with relativeefficiency and small loss of charge. Examples of electron transportmaterials which can be used in the optional electron transport layer140, include metal chelated oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (AlQ),bis(2-methyl-8-quinolinolato)(p-phenylphenolato) aluminum (BAlq),tetrakis-(8-hydroxyquinolato)hafnium (HfQ) andtetrakis-(8-hydroxyquinolato)zirconium (ZrQ); and azole compounds suchas 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD),3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), and1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivativessuch as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthrolines such as4,7-diphenyl-1,10-phenanthroline (DPA) and2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); and mixturesthereof.

The cathode 160, is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode can be anymetal or nonmetal having a lower work function than the anode. Materialsfor the cathode can be selected from alkali metals of Group 1 (e.g., Li,Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, includingthe rare earth elements and lanthanides, and the actinides. Materialssuch as aluminum, indium, calcium, barium, samarium and magnesium, aswell as combinations, can be used. Li-containing organometalliccompounds, LiF, and Li₂O can also be deposited between the organic layer150 and the cathode layer 160 to lower the operating voltage. Thislayer, not shown, may be referred to as an electron injection layer.

c. Device Fabrication

The device layers can be formed by any deposition technique, orcombinations of techniques, including vapor deposition, liquiddeposition, and thermal transfer.

In some embodiments, the device is fabricated by liquid deposition ofthe buffer layer, the hole transport layer, and the photoactive layer,and by vapor deposition of the anode, the electron transport layer, anelectron injection layer and the cathode.

The buffer layer can be deposited from any liquid medium in which it isdissolved or dispersed and from which it will form a film. In oneembodiment, the liquid medium consists essentially of one or moreorganic solvents. In one embodiment, the liquid medium consistsessentially of water or water and an organic solvent. In one embodimentthe organic solvent is selected from the group consisting of alcohols,ketones, cyclic ethers, and polyols. In one embodiment, the organicliquid is selected from dimethylacetamide (“DMAc”), N-methylpyrrolidone(“NMP”), dimethylformamide (“DMF”), ethylene glycol (“EG”), aliphaticalcohols, and mixtures thereof. The buffer material can be present inthe liquid medium in an amount from 0.5 to 10 percent by weight. Otherweight percentages of buffer material may be used depending upon theliquid medium. The buffer layer can be applied by any continuous ordiscontinuous liquid deposition technique. In one embodiment, the bufferlayer is applied by spin coating. In one embodiment, the buffer layer isapplied by ink jet printing. After liquid deposition, the liquid mediumcan be removed in air, in an inert atmosphere, or by vacuum, at roomtemperature or with heating. In one embodiment, the layer is heated to atemperature less than 275° C. In one embodiment, the heating temperatureis between 100° C. and 275° C. In one embodiment, the heatingtemperature is between 100° C. and 120° C. In one embodiment, theheating temperature is between 120° C. and 140° C. In one embodiment,the heating temperature is between 140° C. and 160° C. In oneembodiment, the heating temperature is between 160° C. and 180° C. Inone embodiment, the heating temperature is between 180° C. and 200° C.In one embodiment, the heating temperature is between 200° C. and 220°C. In one embodiment, the heating temperature is between 190° C. and220° C. In one embodiment, the heating temperature is between 220° C.and 240° C. In one embodiment, the heating temperature is between 240°C. and 260° C. In one embodiment, the heating temperature is between260° C. and 275° C. The heating time is dependent upon the temperature,and is generally between 5 and 60 minutes. In one embodiment, the finallayer thickness is between 5 and 200 nm. In one embodiment, the finallayer thickness is between 5 and 40 nm. In one embodiment, the finallayer thickness is between 40 and 80 nm. In one embodiment, the finallayer thickness is between 80 and 120 nm. In one embodiment, the finallayer thickness is between 120 and 160 nm. In one embodiment, the finallayer thickness is between 160 and 200 nm.

The hole transport layer can be deposited from any liquid medium inwhich it is dissolved or dispersed and from which it will form a film.In one embodiment, the liquid medium consists essentially of one or moreorganic solvents. In one embodiment, the liquid medium consistsessentially of water or water and an organic solvent. In one embodimentthe organic solvent is an aromatic solvent. In one embodiment, theorganic liquid is selected from chloroform, dichloromethane, toluene,xylene, mesitylene, anisole, and mixtures thereof. The hole transportmaterial can be present in the liquid medium in a concentration of 0.2to 2 percent by weight. Other weight percentages of hole transportmaterial may be used depending upon the liquid medium. The holetransport layer can be applied by any continuous or discontinuous liquiddeposition technique. In one embodiment, the hole transport layer isapplied by spin coating. In one embodiment, the hole transport layer isapplied by ink jet printing. After liquid deposition, the liquid mediumcan be removed in air, in an inert atmosphere, or by vacuum, at roomtemperature or with heating. In one embodiment, the layer is heated to atemperature of 300° C. or less. In one embodiment, the heatingtemperature is between 170° C. and 275° C. In one embodiment, theheating temperature is between 170° C. and 200° C. In one embodiment,the heating temperature is between 190° C. and 220° C. In oneembodiment, the heating temperature is between 210° C. and 240° C. Inone embodiment, the heating temperature is between 230° C. and 270° C.In one embodiment, the heating temperature is between 270° C. and 300°C. The heating time is dependent upon the temperature, and is generallybetween 5 and 60 minutes. In one embodiment, the final layer thicknessis between 5 and 50 nm. In one embodiment, the final layer thickness isbetween 5 and 15 nm. In one embodiment, the final layer thickness isbetween 15 and 25 nm. In one embodiment, the final layer thickness isbetween 25 and 35 nm. In one embodiment, the final layer thickness isbetween 35 and 50 nm.

The photoactive layer can be deposited from any liquid medium in whichit is dissolved or dispersed and from which it will form a film. In oneembodiment, the liquid medium consists essentially of one or moreorganic solvents. In one embodiment, the liquid medium consistsessentially of water or water and an organic solvent. In one embodimentthe organic solvent is an aromatic solvent. In one embodiment, theorganic solvent is selected from chloroform, dichloromethane, toluene,anisole, 2-butanone, 3-pentanone, butyl acetate, acetone, xylene,mesitylene, chlorobenzene, tetrahydrofuran, diethyl ether,trifluorotoluene, and mixtures thereof. The photoactive material can bepresent in the liquid medium in a concentration of 0.2 to 2 percent byweight. Other weight percentages of photoactive material may be useddepending upon the liquid medium. The photoactive layer can be appliedby any continuous or discontinuous liquid deposition technique. In oneembodiment, the photoactive layer is applied by spin coating. In oneembodiment, the photoactive layer is applied by ink jet printing. Afterliquid deposition, the liquid medium can be removed in air, in an inertatmosphere, or by vacuum, at room temperature or with heating. Optimalbaking conditions depend on the vapor pressure properties of the liquidsbeing removed and their molecular interaction with the liquids. In oneembodiment, the deposited layer is heated to a temperature that isgreater than the Tg of the material having the highest Tg. In oneembodiment, the deposited layer is heated between 10 and 20° C. higherthan the Tg of the material having the highest Tg. In one embodiment,the deposited layer is heated to a temperature that is less than the Tgof the material having the lowest Tg. In one embodiment, the heatingtemperature is at least 10° C. less than the lowest Tg. In oneembodiment, the heating temperature is at least 20° C. less than thelowest Tg. In one embodiment, the heating temperature is at least 30° C.less than the lowest Tg. In one embodiment, the heating temperature isbetween 50° C. and 150° C. In one embodiment, the heating temperature isbetween 50° C. and 75° C. In one embodiment, the heating temperature isbetween 75° C. and 100° C. In one embodiment, the heating temperature isbetween 100° C. and 125° C. In one embodiment, the heating temperatureis between 125° C. and 150° C. The heating time is dependent upon thetemperature, and is generally between 5 and 60 minutes. In oneembodiment, the final layer thickness is between 25 and 100 nm. In oneembodiment, the final layer thickness is between 25 and 40 nm. In oneembodiment, the final layer thickness is between 40 and 65 nm. In oneembodiment, the final layer thickness is between 65 and 80 nm. In oneembodiment, the final layer thickness is between 80 and 100 nm.

The electron transport layer can be deposited by any vapor depositionmethod. In one embodiment, it is deposited by thermal evaporation undervacuum. In one embodiment, the final layer thickness is between 1 and100 nm. In one embodiment, the final layer thickness is between 1 and 15nm. In one embodiment, the final layer thickness is between 15 and 30nm. In one embodiment, the final layer thickness is between 30 and 45nm. In one embodiment, the final layer thickness is between 45 and 60nm. In one embodiment, the final layer thickness is between 60 and 75nm. In one embodiment, the final layer thickness is between 75 and 90nm. In one embodiment, the final layer thickness is between 90 and 100nm.

The electron injection layer can be deposited by any vapor depositionmethod. In one embodiment, it is deposited by thermal evaporation undervacuum. In one embodiment, the vacuum is less than 10⁻⁶ torr. In oneembodiment, the vacuum is less than 10⁻⁷ torr. In one embodiment, thevacuum is less than 10⁻⁸ torr. In one embodiment, the material is heatedto a temperature in the range of 100° C. to 400° C.; 150° C. to 350° C.preferably. The vapor deposition rates given herein are in units ofAngstroms per second. In one embodiment, the material is deposited at arate of 0.5 to 10 Å/sec. In one embodiment, the material is deposited ata rate of 0.5 to 1 Å/sec. In one embodiment, the material is depositedat a rate of 1 to 2 Å/sec. In one embodiment, the material is depositedat a rate of 2 to 3 Å/sec. In one embodiment, the material is depositedat a rate of 3 to 4 Å/sec. In one embodiment, the material is depositedat a rate of 4 to 5 Å/sec. In one embodiment, the material is depositedat a rate of 5 to 6 Å/sec. In one embodiment, the material is depositedat a rate of 6 to 7 Å/sec. In one embodiment, the material is depositedat a rate of 7 to 8 Å/sec. In one embodiment, the material is depositedat a rate of 8 to 9 Å/sec. In one embodiment, the material is depositedat a rate of 9 to 10 Å/sec. In one embodiment, the final layer thicknessis between 0.1 and 3 nm. In one embodiment, the final layer thickness isbetween 0.1 and 1 nm. In one embodiment, the final layer thickness isbetween 1 and 2 nm. In one embodiment, the final layer thickness isbetween 2 and 3 nm.

The cathode can be deposited by any vapor deposition method. In oneembodiment, it is deposited by thermal evaporation under vacuum. In oneembodiment, the vacuum is less than 10⁻⁶ torr. In one embodiment, thevacuum is less than 10⁻⁷ torr. In one embodiment, the vacuum is lessthan 10⁻⁸ torr. In one embodiment, the material is heated to atemperature in the range of 100° C. to 400° C.; 150° C. to 350° C.preferably. In one embodiment, the material is deposited at a rate of0.5 to 10 Å/sec. In one embodiment, the material is deposited at a rateof 0.5 to 1 Å/sec. In one embodiment, the material is deposited at arate of 1 to 2 Å/sec. In one embodiment, the material is deposited at arate of 2 to 3 Å/sec. In one embodiment, the material is deposited at arate of 3 to 4 Å/sec. In one embodiment, the material is deposited at arate of 4 to 5 Å/sec. In one embodiment, the material is deposited at arate of 5 to 6 Å/sec. In one embodiment, the material is deposited at arate of 6 to 7 Å/sec. In one embodiment, the material is deposited at arate of 7 to 8 Å/sec. In one embodiment, the material is deposited at arate of 8 to 9 Å/sec. In one embodiment, the material is deposited at arate of 9 to 10 Å/sec. In one embodiment, the final layer thickness isbetween 10 and 10000 nm. In one embodiment, the final layer thickness isbetween 10 and 1000 nm. In one embodiment, the final layer thickness isbetween 10 and 50 nm. In one embodiment, the final layer thickness isbetween 50 and 100 nm. In one embodiment, the final layer thickness isbetween 100 and 200 nm. In one embodiment, the final layer thickness isbetween 200 and 300 nm. In one embodiment, the final layer thickness isbetween 300 and 400 nm. In one embodiment, the final layer thickness isbetween 400 and 500 nm. In one embodiment, the final layer thickness isbetween 500 and 600 nm. In one embodiment, the final layer thickness isbetween 600 and 700 nm. In one embodiment, the final layer thickness isbetween 700 and 800 nm. In one embodiment, the final layer thickness isbetween 800 and 900 nm. In one embodiment, the final layer thickness isbetween 900 and 1000 nm. In one embodiment, the final layer thickness isbetween 1000 and 2000 nm. In one embodiment, the final layer thicknessis between 2000 and 3000 nm. In one embodiment, the final layerthickness is between 3000 and 4000 nm. In one embodiment, the finallayer thickness is between 4000 and 5000 nm. In one embodiment, thefinal layer thickness is between 5000 and 6000 nm. In one embodiment,the final layer thickness is between 6000 and 7000 nm. In oneembodiment, the final layer thickness is between 7000 and 8000 nm. Inone embodiment, the final layer thickness is between 8000 and 9000 nm.In one embodiment, the final layer thickness is between 9000 and 10000nm.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Examples 1-4

The general scheme for preparing electroactive Compounds 1, 3, 4, and 6is shown below.

This examples illustrate the preparation of electroactive compounds 1,3, 4, 6

Example 1

This example illustrates the preparation of Compound 1.

a. Preparation of Intermediate A

Into a RBF (500 mL) was added 2,6-dihydroxnaphthalene (16 g, 0.1 mole),K2CO3 (56 g, 0.4 mole) and 2-bromo-1-phenylethanone (40 g, 0.2 mole)dissolved in 300 mL acetone. The mixture was refluxed 48 h. A whiteprecipitate was formed and it was filtered and the solid was washed withacetone twice (50 mL×2). The filtrate was tested by TLC (Hexane:ethylacetate 1:2), and it showed a trace amount of the impurities, nostarting materials were found. (Rf: 2,6-dihydroxnaphthalene: 0.1, Rf:2-bromo-1-phenylethanon: 0.7). The white solid was then washed withwater twice (200 mL each) and then with diluted HCl (5% 200 mL),followed with water again to get rid of inorganic salts. After washedwith acetone, the white compound was dried to afford 35 g compound A(yield: 88%). C₂₆H₂₀O₄: EI, MS m/z (%): 396 (100, M⁺).

b. Preparation of Compound 1

Into a RBF (500 mL) was added intermediate A (30 g, 0.0757 mole), CH₂Cl₂(2300 mL), cooled down about to 5° C. using ice-water bath. CH₃SO₃H (50g, 0.5 mole) was added dropwise and keep the temperature below 10° C.The suspension mixture became pink color then dark brown solution. Itwas stirred at room temperature for 12 h. TLC (in Hexane:ethyl acetate10:1) gives a bluish brown-color spot (Rf: 0.7), clearly indicated thenew material was produced. (Rf: 2,6-dihydroxnaphthalene: 0.01, Rf:2-bromo-1-phenylethanon: 0.5). Run flash column using CH₂Cl₂ as eluentto get a pure product (24.5 g, 90% yield). The compound is thermalstable up to 350° C. The melting point is at 340-5° C. ¹H NMR (CDCl₃,ref: δ 7.26 ppm, 500 MHz): δ 7.95-93 ppm (d, 2H, J=9.0 Hz), 7.66 ppm (s,2H), 7.61-7.60 ppm (dd, 4H, J1=8.5 Hz, J2=1.9 Hz), 7.55-7.45 ppm (m,8H); ¹³C NMR (ppm): 152.3, 142.0, 133.3, 130.0, 128.7, 127.9, 125.4,124.3, 121.9, 121.0, 112.0. C₂₆H₁₆O₂: EI, MS m/z (%): 360 (100, M⁺).

Example 2

This example illustrates the preparation of Compound 3.

a. Preparation of Intermediate C

Into a RBF (250 mL) was added a chloroform (100 mL) and acetic acid (20mL) Compound 1 (3.6 g, 0.01 mole), was added in one portion ofN-bromosuccinimide (“NBS”) (3.6 g, 0.021 mole). The mixture was refluxedfor 2 h. First, a clear solution was formed. Then 1 h later a lightyellow precipitate came out. Continue reflux for 1 h until the startingmaterial was gone, tested by TLC (Hexane:ethyl acetate 1:2), and itshowed a trace amount of the impurities, no starting materials werefound. Cooled down the reaction mixture, and added water. The organicphase was separated, which was washed three times by water (30 mL each).The organic phase was then concentrated until 10 mL solvent present,then added hexane and the light yellow powder was formed. It was thenwashed with hexane and recrystallized from chloroform and hexane to give4.6 g product. (Yield: 89%). ¹H NMR (CDCl₃, ref: δ 7.26 ppm, 500 MHz): δ7.68-66 ppm (d, 2H, J=9.1 Hz), 7.59-7.52 ppm (m, 10H), 7.48-7.46 ppm (d,2H, J=9.1 Hz). ¹³C NMR (ppm): 152.4, 132.4, 130.4, 128.9, 128.5, 126.7,124.5, 123.2, 122.9, 120.5, 111.6. C₂₆H₁₄Br₂O₂: EI, MS m/z (%): 518(100, M⁺).b. Preparation of Compound 3

Into a RBF (250 mL) was added intermediate C (3.6 g, 0.007 mole),1-naphthalenyl boronic acid (2.6 g, 0.015 mol), followed by the additionof toluene (60 mL). The mixture was purged with N₂ for 10 min. Then 2 NNa₂CO₃ (3.0 g, 0.03 mole) dissolved in the water (15 mL) was added. Aphase catalyst Aliquat® 336 (registered trademark of Cognis Corp.) wasadded. The mixture was continue to purge with N₂ for 10 min. A catalystamount of Pd(PPh₃)₄ (0.35 g) was added. The mixture was refluxed for 12h. First, a clear solution was formed (in about 0.5 h). Then 1 h later alight yellow precipitate was appeared. Continue reflux for overnight. Aslightly dark yellow precipitate was observed. Cooled down the reactionmixture, then poured the mixture into methanol (200 mL). The precipitatewas filtered, and the solid was washed with methanol then washed withwater three times (100 mL each). It was further washed with methanol andacetone, ether and dried. A white deep blue fluorescent powder wasformed (4.2 g, yield: 99%). The compound was further purified by threezone submission to give a pure product. C₄₈H₂₈O₂: EI, MS m/z (%): 612(100, M⁺).

Example 3

Similar synthetic methods were used to prepare Compound 4.

Into a RBF (5000 mL) was added Intermediate C (109.1, 0.21 mol),4-tert-butyl phenylboronic acid (90 g, 0.51 mol), followed by theaddition of toluene (2600 mL). The mixture was purged with N₂ for 10min. Then Na₂CO₃ (118.8 g, 1.055 mole) dissolved in the water (520 mL)was added. The mixture was continued to be purged with N₂ for 10 min. Acatalytic amount of Pd(PPh₃)₄ (1.7 g) was added. The mixture wasrefluxed for 12 h. First, a clear solution was formed (in about 2 h).Then 2 h later a light white precipitate was formed. Continue reflux forovernight. A slightly white precipitate was formed. Cooled down thereaction mixture to 40° C., filtered, the solid was stirred with hottoluene (200 ml) for 12 h and hot THF/CH₂Cl₂ (100 ml/100 ml) for 12 h.Filtered and washed with THF and dried. An off-white powder was formed(115 g, yield: 87.6%). Further purification using three-zone sublimationgives a pure product. ¹H NMR (CDCl₃, ref: δ 7.26 ppm, 500 MHz): δ7.63-7.61 ppm (m, 10 H), 7.50-7.48 ppm (m, 8H), 7.32-7.28 ppm (m, 4H),2.42 ppm (m, 2 H), 1.28 ppm (s, 18H). C₄₆H₄₀O₂ EI, MS m/z (%): 6243(100%, M⁺).

Example 4

Similar synthetic methods were used to prepare Compound 6.

Into a RBF (250 mL) was added Intermediate C (3.8 g, 0.0075 mole),1-naphthalenyl boronic acid (3.9 g, 0.015 mol), followed by the additionof toluene (60 mL). The mixture was purged with N₂ for 10 min. Then 2 NNa₂CO₃ (3.0 g, 0.03 mole) dissolved in the water (15 mL) was added. Aphase catalyst Aliquat®336 was added. The mixture was continued to bepurged with N₂ for 10 min. A catalytic amount of Pd(PPh₃)₄ (0.35 g) wasadded. The mixture was refluxed for 12 h. A slightly dark yellowprecipitate was observed. Cooled down the reaction mixture, then pouredthe mixture into methanol (200 mL). The precipitate was filtered, andthe solid was washed with methanol then washed with water three times(100 mL each). It was further washed with methanol and acetone, etherand dried. A white deep blue fluorescent powder was formed (5.1 g,yield: 90%). The compound was further purified by three zone submissionto give a pure white product. It shows a bright deep blue fluorescentemission with CIE (0.161, 0.026) at diluted toluene solution. Thecompound is thermal stable up to 360° C. The melting point is at 340-5°C. ¹H NMR (CDCl₃, ref: δ 7.26 ppm, 500 MHz): δ 7.70-7.68 ppm (d, 2H,J=8.3 Hz), 7.58 ppm (m, 10H), 7.47 ppm (m, 6H), 7.15-7.13 ppm (m, 2H,J=7.5 Hz), 7.10-7.08 ppm (d, 2H, J=8.2 Hz), 2.42 ppm (m, 2H), 1.84 ppm(m, 8H), 1.42-1.18 ppm (m, 14H), 1.06-1.00 ppm (m, 4H), 0.90-0.86 ppm(t, 6H, J=7.5 Hz). EI, MS m/z (%): 760.43 (100%, M+).

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.The use of numerical values in the various ranges specified herein isstated as approximations as though the minimum and maximum values withinthe stated ranges were both being preceded by the word “about.” In thismanner slight variations above and below the stated ranges can be usedto achieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding every value between the minimum and maximum average valuesincluding fractional values that can result when some of components ofone value are mixed with those of different value. Moreover, whenbroader and narrower ranges are disclosed, it is within thecontemplation of this invention to match a minimum value from one rangewith a maximum value from another range and vice versa.

1. An electroactive material having Formula I:

wherein: Q is the same or different at each occurrence and isindependently selected from the group consisting of O, S, SO, SO₂, Se,Te, NR, BR, PR, PO, PO₂, and SiR₂; R is the same or different at eachoccurrence and is independently selected from the group consisting ofhydrogen, alkyl, aryl, alkenyl, and alkynyl; R¹ through R⁸ are the sameor different and are independently selected from the group consisting ofhydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl,alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO₃R₂,—OPO₃R₂, and CN.
 2. The electroactive material of claim 1, wherein Q isO.
 3. The electroactive material of claim 1, wherein at least one of R²and R⁴ is selected from the group consisting of alkyl, aryl, anddiarylamino.
 4. The electroactive material of claim 1, wherein at leastone of R¹ and R³ are selected from the group consisting of alkyl, aryl,and diarylamino.
 5. The electroactive material of claim 1, wherein atleast one of R⁵, R⁶, R⁷, and R⁸ is selected from the group consisting ofalkyl, aryl, and diarylamino.
 6. The electroactive material of claim 1,selected from the group consisting of Compound 1 through Compound 13:


7. An electroactive polymer having at least one monomeric unit selectedfrom the group consisting of Formula II, Formula III, and combinationsthereof:

wherein: Ar is the same or different at each occurrence and is anaromatic unit; Q is the same or different at each occurrence and isindependently selected from the group consisting of O, S, SO, SO₂, Se,Te, NR, BR, PR, PO, PO₂, and SiR₂; R is the same or different at eachoccurrence and is independently selected from the group consisting ofhydrogen, alkyl, aryl, alkenyl, and alkynyl; and R¹ through R⁸ are thesame or different and are independently selected from the groupconsisting of hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy,alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR,—PO₃R₂, —OPO₃R₂, and CN.
 8. The polymer of claim 7, wherein the polymeris a homopolymer.
 9. The polymer of claim 7, having Formula IV or V:

wherein: Ar is the same or different at each occurrence and is anaromatic unit; Q is the same or different at each occurrence and isindependently selected from the group consisting of O, S, SO, SO₂, Se,Te, NR, BR, PR, PO, PO₂, and SiR₂; R is the same or different at eachoccurrence and is independently selected from the group consisting ofhydrogen, alkyl, aryl, alkenyl, and alkynyl; R¹ through R⁸ are the sameor different and are independently selected from the group consisting ofhydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl,alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO₃R₂,—OPO₃R₂, and CN; and a and b represent mole fractions, such that a+b=1.10. The polymer of claim 9, wherein Ar is selected from the groupconsisting of phenylene, naphthylene, biphenylene, binaphthylene,anthracenylene, fluorenylene, diarylamine and combinations thereof. 11.The polymer of claim 9 selected from the group consisting of Compound 14through Compound 18:


12. An organic electronic device comprising a first electrical contact,a second electrical contact and an electroactive layer therebetween, theelectroactive layer comprising an electroactive material selected fromthe group consisting of a compound having Formula I and a polymer havingat least one monomeric unit selected from the group consisting ofFormula II, Formula III, and combinations thereof:

wherein: Q is the same or different at each occurrence and isindependently selected from the group consisting of O, S, SO, SO₂, Se,Te, NR, BR, PR, PO, PO₂, and SiR₂; R is the same or different at eachoccurrence and is independently selected from the group consisting ofhydrogen, alkyl, aryl, alkenyl, and alkynyl; and R¹ through R⁸ are thesame or different and are independently selected from the groupconsisting of hydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy,alkenyl, alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR,—PO₃R₂, —OPO₃R₂, and CN.
 13. The device of claim 12, wherein the polymerhas Formula IV or Formula V:

wherein: Ar is the same or different at each occurrence and is anaromatic unit; Q is the same or different at each occurrence and isindependently selected from the group consisting of O, S, SO, SO₂, Se,Te, NR, BR, PR, PO, PO₂, and SiR₂; R is the same or different at eachoccurrence and is independently selected from the group consisting ofhydrogen, alkyl, aryl, alkenyl, and alkynyl; R¹ through R⁸ are the sameor different and are independently selected from the group consisting ofhydrogen, alkyl, aryl, halogen, hydroxyl, aryloxy, alkoxy, alkenyl,alkynyl, amino, alkylthio, phosphino, silyl, —COR, —COOR, —PO₃R₂,—OPO₃R₂, and CN; and a and b represent mole fractions, such that a+b=1.14. The device of claim 12, wherein the electroactive layer is a chargetransport layer.
 15. The device of claim 14, wherein the chargetransport layer is a hole transport layer.
 16. The device of claim 12,wherein the electroactive layer is a photoactive layer.
 17. The deviceof claim 16, wherein the photoactive layer further comprises a hostmaterial.
 18. The device of claim 16, wherein the photoactive layerfurther comprises a photoactive material.